Method of reactivating desulphurizing agents for hydrocarbon oils



' March 29 1927 J. B. RATHER ET Ax. y

METHOD OF REACIIVATING DESULPHURIZING AGENTS FOR 4.HYDROCARBON OILS Original Filed April 16. 1924 2 Sheets-Sheet l INVIEIVTORy BY A ATTORNEY 1622,671 March 29 1927' J. B. RATHER ET AL METHOD OF REACTIVATING DESULPHURIZING AGENTS FOR'HYDROCARBON OILS originaliled April 16. 1924 sheets-sheet 2 I ,fa/yer @afer 2j esulpuria';

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I/or Zine y n Z7 0 candenwe'r l Patented Main. Z9, i927,

JAMES E. RATHER, or BROOKLYN,

NEW YORK, ASSIGNORS TO STANDARD OIL YORK, N. Y., A CORIORATION OF NEW YORK.

AND FREDERICK s. SHEPARD, E NEW ROCHELLE,

COMPANY 0F NEW YORK, DE NEW METHOD 0E EEACTIVATING DEsULrHURrziNG AGENTS Foa EYDEocARBoN oILs.

Application ilet April 16, 17924,' Serial N0. 706,858. Renewed August AWhen' certain materials, such as metallic oxides, are used a: desulphurizing agents for -desulphurizing hydrocarbon oils, their activity becomes impaired after a while 011 account of taking up sulphur from the treated oil. A. process for desulphurizing hydrocarbon oils, using such materials as desulphurizing agents, is disclosed in a copending application filed by James B. Rather, Leslie C. BeardJ Jr., and Thomas M. Berry on even date herewith, Serial No. 706,815.

The present invention relates to a method of reactivating, or restoring to their original oxide condition and activity, metallic'oxides after their aetivity has been impaired as'a result of their use as desulphurizing agents for hydrocarbon oils. y v

Prior processes for desulphurizing. hydrocarbon oils require desulphurizing materials in particles not larger than 200 mesh, and leave the desulphurizing materials mixed with a considerable amount of the oil re siduum, lat the end of a run, andin order to 'reactivate the desulphurizing materials, t-he oil must be pressed out, leaving a cake of the desulphurizmg material which mustv be burned to remove the sulphur compounds, and must be subsequently ground to 200 mesh before it is suitable to be used in such process for another run. These methods of reactivating the desulphurizing materials have required separate apparatus, 'suchA as filters, retorts, grinders, etc., and the removal of the materials to such apparatus for treatment, with consequent losses, expense and delay. After reactivation they must be replaced in the oil desulphurizing apparatus Much handling and moving about of the materials has been required, as well expensive apparatus. y

The principal object of .our invention is' to provide a method ,of .reactivating certain metallic oxides after they have been used as desulphurizing agents for desulphurizing hydrocarbon oils, and to provide a method `which is safe and simple to follow, which does 4not re apparatus, and which may be carried out quickly, inexpensively and4 eiiciently.

1 ,Aurther object'of our`invent-ion is tol provide a method of reactivating desulphur- 4iz'in'g' materials,such"as metallic oxides after 1) use as desulphurizing agents for hydrocarbon oils, whlch does not require the removal as cumbersome and actlvatmg the desulphurizing materials used quire dangerously complicated` 0f the desulphurizing materials .from the apparatus in which they are contained while acting as desulphurizing agents for hydrocarbon oils, and which does not require the .desulphurizing agents to be moved about or removed to separate apparatus.

A further object of our invention is to provide a process for desulphurizing hydrocarbonoils by-means of desulphurizing materials, such as metallic oxides, and to provide a method of reactivating the desulphurizing materials after they have beenv used in carrying out such process, which process and method may be carried out in the same apparatus without necessitating any handling or removal ofthe desulphurizing materials, and a further object of our invention is to provide an apparatus adapted for use in carrying out both the process of desulphur# izing hydrocarbon oils and the method of reactivating the desulphurizing materials used in the process. Y

Other objectsvof our invention willbe in part obvious and in part vpointed out herelnafter. v

-The invention accordingly consists in the several steps and the relation to each of the others thereof which will' be exemplified in the hereinafter disclosed. method, and the scope of the application of which will be indicated in the claims that follow.

In order that a clearer understanding of our invention may be had, attention is hereby'directed to the accompanying drawings,4

forming a part of this application and illustrating diagrammatically certain apparatus adapted for use in carrying out our process for desulphurizing hydrocarbon oils also in carrying out our method of rein the oil desulphurizing process. Referring to the drawings, Fig. l is a diagrammatic layout of suchzan apparatus; Fig. 2 is a4 diagrammatic layout of suchan apparatus in a modified diagrammatic layout .of such an apparatus in still another form. j

Similar reference characters refer tosimi-l 'lar parts throughout the several views of the drawings.

`With a preferred form of apparatus (Fig. we ca-rrylout our process by vaporizing the oil to be treated in a still l of conventional design, and conducting the oil vapors form; and Fig. 3 'is a l from the still -through t closed receptacle 2, such as a tower, which i in a mass on the plate 4 within the inner comprises a closed outer shell, insulated as at 3, and an inner shell, having its bottom and walls spaced from the outer shell, ferming an outer compartment 6 betweenl the shells. The conduit 5 leads to` the vapor inlet located between the bottoms of the two shells of the cabinet. Preferably a. perforated plate 4 -is mounted in the inner shell, and the vaporoutlet from the tower is situated between the plate 4 and the bottom of the inner shell and communicates with exit pipe 8 which lea-ds to .a suitable condenser. The desulphurizing agents, which may be copper oxide or other metallic oxides, and which are preferablyl in the form of articles'larger than 100 mesh, aresupported shell of the tower. The desulphurizing ma'- terial is preferably substantially dry, and

- it may or may not be distributed over or mixed with inert material serving as a framework. Such inert material may be,

fullers earth, ypumice, or any other porous substance.

The oil vapors from the still 1 enter the' tower at the conduit ,5,

dow upward through the compartment 6,v then downward through the desulphurizing material in 'the inner shell, intothe space 7 below the p1ate4, and outof the tower through the conduit 8, forv treatment and disposal in the well known manner. The vapors leaving the tower are in satisfactory desulphurized condition.` Preferably, there is a return conduit or pipe Qleading from the bottom of chamber 6 to the still 1, whereby liquid products, formed by the condensing of the oil vapors or otherwise, are led back into the still. `The various conduits may be provided with the usual valves, such as 10, 11 and 12.

For the purpose of vating the desulphurizing material contained in the tower 2, we provide a superheater 13,

of conventional design, which has an outlet pipe 14 communicating with the pipe 5.

Pipe 414 has a suitable valve 15, whichl is normally closed during a run. When it is desired to lrevivify the desulphurizing agents, it is not necessary to remove these agents from the tower to a separate apparatus, a's has been the practice heretofore, but they may is now opened and steam 1s passed from the superh'eater into the compartment 610i the revivifying or reactif be left in the tower and may 'be' reactivated by proper treatment without tower,from which it flows downwardly through the tower and the desulphurizing agentsetherein', and out at the pipe 16. This flow. of steam is continued until the last traces of oil vapor are removed from the tower. Then superheated steam is passed from the superheater through the tower until the temperature of the contents of the tower compartment are about 500 degrees `ahrenheit. Then superheate-d air at approximately the same temperature is passed from the superheater through the tower. By this process the desulphurizing agents in the tower, which after a run are sulphides, give up their sulphur components in the form of sulphur dioxide, tower with the air. After the removal of the sulphur dioxide, the passage of superheated air is continued from the superheater 13 until any reduced copper or other metal is converted to the original condition of the oxide. v

The useof superheated steam is not essential, though preferable, and superheated air alone maybe used. The superheating of the steam or air, or both, may be accomplished in any suitable manner, either by heating the tower 'or by heating the steam or air, or both, before they reach the tower.

Referring to Fig. 2, instead of leadin oil vaporsrfrom a still into the bottom o an outer compartment, such-as 6, in a tower 2, as shown in Fig. 1, the oil vapor may be directed through a conduit 20 directly into the top of a closed receptacle 21 so as to flow downwardly through the desulphurizing agents contained therein, and past the perforated plate 22 and out at the outlet pipe 23. Pipe 2,0 has a valve 24, and pipe 23 has a valve 25. A run-back pipe 26 is adapted to return liquids formedl in the tower 21 to the still 1. This pipe has a valve 27. The superheater 13' may haveits outlet pipe 14 leading into the bottom of the tower so that superheated steam and air may be passed from the superheater 13 upwardly through the tower 21 and out at. the exhaust pipe 28 which leads from the which passes from thepipe'20. Pipe' 28 has a valve 29 which isl normally closed .during a run. The valve 24 of pipe 2O and the valve 25 of pipe 23 and the valve 27 of 'pipe 26 are all closed during* the step of reactivating the desulphurizing material'V in the tower 21 after a run. The revivifying or reactivatng step of the process is carried out lin the manner 'described heretofore by means of steam and air, or air alone, passed from the superheater through the tower until all traces of oil vapor and sulphur dioxide are removed from the tower andthe desulphurizing materials are restored to their original condition.

Referring to Fig.l 3, instead of passing the oil vapors downwardly through a tower containing the desulphurizing materials, these f ratus is also adapted to be used heater oil vapors may be passed upwardly through the tower containing such materials. 'io this end, the apparatus, as shown in Fig. 3, includesa pipe leading from the still l into a vapor chamber 3l formed in the bottom of a tower 32 below a suitably mounted perforated plate 33 therein, so that oil vapor may flow from the still upwardly through the desulphurizing agents in the tower and out through to a lsuitable condenser. preferably insulated, as at 35.

flhe tower 32 is r:this appato revivify or to reactivate the desulphurizing agents in the tower 32. To this end, the super- 13, by means of pipe 36, communicates with `the conduit 30 andv the outlet pipe 34y has 'an exhaust pipe 37. The steam and air, or air alone is through the tower, first to remove all traces ot' the oil vapor, and then to produce sulphur dioxide from the copper or other sulphides and to convert anyv reduced copper or other metal to the original condition of the oxide. The valve 38 of pipe 30 and the valve 39 of pipe 34: are open for a run ol:'

oil and are closed during the reactivating y step. The valve 40 of pipe 36 and the valve CII 4l ot' pipe 37 are closed during a run of oil and are open for the reactivatin'; step.

It will be readily apparent from the above that the process isfsait'e, simple, economical and fast, and may be carried out with a simpie apparatus, without requiring mechanical stirrers, and without requiring removal or transference of the desulphurizing material to condition 'he apparatus for another run.

As many changes could be made in the construction of apparatus described, and as many apparently widely dili'erent embodiments or' this invention could be made without departing from the scope thereof, it is intended that the mattei' contained in the above description or shown in the accompanying drawings be interpreted as lllustrative and not in a limiting sense.

'lhe above disclosed process for desulphurizing hydrocarbon oils is claimed in an 'application filed by James B. Rather, Leslie C. Beard, Jr., and Thomas M. Berry on even date herewith, Serial No. 706,815.

Whatwe claim` iszl. rlhe process of desulphurizing metallic sulphides carrying oil, which includes rethe outlet pipe 34:'`

passed upwardlymoving the oil from the sulphides without burning the oil, and then converting the metallic sulphides to metallic oxides.

2. The process of desulphurizing metallic sulphides carrying oil, as obtained by subjecting metallic oxides to sulphurous oil vapors, which consists of first removing the oil from said sulphides, and then subjecting the metallic sulphides to a current of air at a temperature sufliciently high to remove the sulphurous elements of .the sulphides in the form of sulphur dioxide.

3. The process of des'ulphurizing metallic sulphides carrying oil, as. obtained by subjecting metallic oxides to sulphurous oil vapors, which consists of lirst removing the oil from said sulphides, and then subjecting the metallic sulphides to a current of air, while maintaining the sulphides and air at a temperature of about 500 degrees Fahrenheit, to remove the sulphurous elements of the sulphidesin the form of sulphur di- 'l oxide.

4. The process of desulphurizing metallic sulphides carrying oil, as obtained by subjecting metallic oxides to sulphurous oil vapors, which consists of first removing the subjecting the oil from said sulphides by metallic sulphides to a current of superheated steam, and then subjecting the sulphides to a current of air, while maintaining the sulphides and air at a temperature ot' about 500 degrees Fahrenheit, to remove the sulphurous elements of the sulphides in the form of sulphur dioxide.

5. rlhe process of desulphurizing metallic sulphides carrying oil, a3 obtained by subjecting metallic oxidesl to sulphurous oil vapors, which consists of first removing the oil from said sulphides by subjecting the metallic sulphides to a current of superheated steam, and then subjecting` the sulphides to a current of air, while maintaining the sulphides. and air at a temperature ot' about 500 degrees Fahrenheit, to remove the sulphurous elements of the sulphides in the .form of sulphur dioxide, and continuing `the current of air at a sufficiently high temperature to convert any resulting metal to metallic` oxide.

rhis specification signed this ilth day of April, 1924.' JAMES B. RATHER. FREDERICK S. SHEPARD. 

